Oriented Assembly of 2D Metal‐Pyridylporphyrinic Framework to Regulate the Redox Kinetics in Li−S Batteries
Abstract
AbstractDeveloping the highly efficient catalysts is a great challenge for accelerating the redox reactions in Li−S batteries. Inspired by the single‐atom catalysts and metalloproteins, it makes full use of the advantages of metal–organic frameworks (MOFs) as electrocatalysts. Herein, a series of 2D metal‐bonded metalloporphyrin MOFs are prepared with 5,10,15,20‐tetrakis(4‐pyridyl) cobalt porphyrin (CoTPyP) as building blocks and transition metals (M═Mn, Fe, Co, Ni, and Cu) as nodes, respectively. The crystalline structures of the bimetallic 2D MOFs are confirmed by UV–vis spectra and X‐ray diffraction analyses. According to DFT calculation, the peripheral metal nodes optimize the electronic state of Co in porphyrin core. Especially, CoTPyP‐Mn facilitates the cleavage of S−S bond from both ends and promotes their conversion kinetics through Co−S and Li−N bonds. The Li−S cells with CoTPyP‐Mn show the initial specific capacity of 1339 mA h g−1 at 0.2 C. The capacity decay rate is only 0.0442% per cycle after 1000 cycles at 2 C. This work achieves the rational control of the central Co d electron state through the peripheral regulation and enriches the application of MOFs in accelerating the redox kinetics in Li−S batteries.
Article Details
Authors (13)
Yan Zhao
Ziyun Shang
School of Mathematics and Physics China University of Geosciences Wuhan China
Muti Feng
School of Mathematics and Physics China University of Geosciences Wuhan 430074 China
Hongxia Zhong
School of Mathematics and Physics, China University of Geosciences (Wuhan) 1 , Wuhan 430074,
Yu Du
Key Laboratory of Material Simulation Methods and Software of Ministry of Education, College of Physics
Weijie Chen
Laboratory of Advanced Optoelectronic Materials, Suzhou Key Laboratory of Novel Semiconductor-optoelectronics Materials and Devices, State Key Laboratory of Bioinspired Interfacial Materials Science, College of Chemistry, Chemical Engineering and Materials Science
Yu Wang
Jiaxing Zou
School of Materials Science and Engineering Zhongyuan Critical Metals Laboratory Zhengzhou University Zhengzhou 450001 China
Yulin Chen
State Key Laboratory of Quantum Functional Materials, School of Physical Science and Technology
Hai Wang
Key Lab of Biomass Chemical Engineering of Ministry of Education and College of Chemical and Biological Engineering
Ye Wang
Jia‐Nan Zhang
School of Materials Science and Engineering Zhengzhou University Zhengzhou China
Gan Qu
School of Materials Science and Engineering Zhongyuan Critical Metals Laboratory Zhengzhou University Zhengzhou China